Process for stripping in butadiene extraction



Sept. 7, 1948. R. A. GlvEN Erm. 2,448,971

PROCESS FOR STRIPPING vIN BUTADIENE EXTRACTION Filed Jan. 4, 1944 f FIL TE l 'FIG-2 Patented Sept., 7, 1.48

Y ammi Y l moeras ron srammo m msnm EXTBACI'ION lucharon.ernanntecharles,1...,smlwnlmn` aci-.fasubsmmnudrmusuuml ilDevelopmentCompany,aeal-pentlano Delaware Application January 4, 1944, Serial No. 516,93.

1 2 Claims. (Cl. 20C-881.5) 2 This invention relates to improvements in the through line 3 and ilows down the tower counterseparation and concentration of diolens from A currently to the hydrocarbon vapors rising in the mixtures of saturated and unsaturated hydrotower. The unabsorbed hydrocarbon vapors carbons containing dioleilns and relates particuleave the top of extractor 2 through line l. The larly to the separation and concentration of buta- 5 solvent leaving the bottom of extractor 2 contains dieneby the use of a cuprous salt solution. dissolved hydrocarbon consisting principally of Organic products obtained on cracking petrodioletln. However. about to 20% of oleilnsare ieum, brown coal, brown coal tar, synthetic paralso dissolved in the solvent and must be selecaiiins and the like in the presence or absence of tively removed. The solvent flows from extractor additional gas or vapors such as steam, hydro- 10 2 through stripper l5 wherein it is contacted gen, nitrogen, carbon dioxide and the like, frecountercurrently with recycled butadiene vapors quently contain both olens and dilens that are introduced into the bottom of stripper l5 through gaseous at ordinary temperatures and pressures. line 5. The olens are stripped from solution and It is very diilicult to separate the gaseous prodthe solvent leaving the bottom of stripper i5 uct into its component parts even by refrigerthrough line i contains essentially only dissolved ation as the boiling points of the said oleiins and dioleiins. Suitable pump means and automatic y diolefins lie very close, for example, in the case valve means may be provided to control the level of butylene and butadiene, the boiling points of of the solution in the stripper and to regulate which are 1 C. and -5 C. A method used exnow from the stripper, as indicated diagramtensively at presentin the separation and concenmatically in Figure 1, and as will be obvious to tration of the oleiln or dioletln is one where a those skilled in the art. This solvent is heated to y solvent is used to extract the desired olefin or 60-90" F. and enters the top of desorber T above diolefln which is thereafter separated from the the to'p plate. This desorber contains either solvent. Asolventusedextensivelyis an aqueous bubble plates or a combination of platesA and solution of ammoniacal cuprous salt. One of the packed sections and is maintained at a. pressure diillculties encountered in using the ammoniacal of 6 to 25 pounds per square inch. A considercuprous salt is that the solution of leither the diable portion of the dimolved dioleiln is ilashed oleiin or olen generally contains a small fraction from solution and passes overhead from desorber of other less soluble ingredients. When butadiene 1 A portion or all of this vapor is recycled is absorbed by aminiacal cuprous acetate, the through une 5 to the bottom of stripper l5 wheresolution contains both the diolefin and a small init strips olenn from the solvent, The partially fraction of the olefin. desorbed solvent passes down through desorber A complication encountered is that in evaporat- 1 and is ooneoted on pan 8; The solvent is withing oi the olen from the solution of dioleiln drown through line l by pump 4l2 and heated to and olen in ammoniacal cuprous acetate. there 15o-180 F. in heat exchanger Il and heater H, is also a tendency for the ammonia to separate, being returned to the tower below pan 8. As inwith the resulting precipitation of'a complex di- (heated in Figure 1, the level of the solvent reolefin-CUPITOUS Salt additiOn product tained in the desorber may be controlled by au- An object of this invention is to selectively sepsomatic valves of any suitabletype. Essentially arate the less soluble olens from an ammoniacal 4o all the dlolenn remaining in solution is rejected cuprous salt solution containing olens and diat this point, These vapors pass up through the oleflns. Another object of this invention is to tower contacting the descending cooler solvent, separate dloleiins without `a substantial loss of and prodnot butadiene vapors are withdrawn ammonia. These and other objects of the invenfrom below the top Plate. Lean solvent leaving tion will be clearly understood upon reading the '45 thebottom of desorber 1, is cooled and recycled to following description with reference to the acabsorber 2 through line l, l

Companyng drawing, Figure 1 showing a ilow Referring to Figure 2, details are shown of the sheet of the process and Figure 2 a sectional proposed system whereby an additional oleiin sketch of the deSOrberstripping stage is obtained in the top of desorber Referring to Figure 1. hydrocarbon feed vapors 1. solvent entering desorber 1 through line t consisting of olefins and diolens plus some other rejeots o oonsideroble portion of the dissolved minor impurities enter extractor 2 through line dlolenn upon entering the tower on the top of I. This tower contains either bubble plates or plate Il, This flashing operation represents a. packed sections end operates atabout 0 pounds portion of o stripping stage since any oleiln reper square inch and 25 F. Ammoniacal cuprous 55 maining in the solvent entering desorber l will acetate solvent enters the top of extractor 2 tendtoboihtl-,hecloiiattllislwillii1 The@ 11H-Shed vapors are recycled to the stripper I5. Solvent flows down desorber 'i and the remainder of the dissolved diolefin together. with ammonia .and

water, is rejected in the hot lower section of the tower. Vapors are withdrawn from below the top plate Il through line I6 and constitute the butadiene product. 'I'hese vapors are then sent to a. water scrubber to remove ammonia. 'I'his ammoniacal cuprous acetatev solution in which the l ammoniacal cuprous acetate solution containmonia is subsequently reconcentrated and returned to the system. in order to maintain the ammonia content of the solvent.

The extraction of butadiene from a dilute butadiene feed using ammoniacal cuprous acetate solvent invloves the followingthree steps:

1. Absorption-In this step, the desired butadiene is dissolved in the solvent along with a small amount of undesired hydrocarbons. This step may be carried out with the hydrocarbon phase in either the liquid or vapor state.

2. Stripping.'-In this step, the undesired hydrocarbons are removed from the solvent, leaving essentially pure butadiene in the solvent. The stripping may be carried out with the hydrocarbon phase in either the liquid or vapor state.

3. Desorption-In. this step, the pure butadieneis recoverd from vthe solvent by vaporiza-l Ation therefrom.

The flashed vapors passy overhead from the desorber and the solvent flows downward from this l top zone to the bottom portion of the desorber wherein the. rest of the butadiene is vaporized` therefrom. The butadiene released in the lower` parts of the desorber is taken from the side of the desorber just beneath the top ash zone. All

or most of the desorber overhead vaporsare recycled to the stripper. All or most ofv the vapors taken from the side go to storage as the product. i

The advantages in using this process are that cold solvent has a higher capacity for' butadiene than does warm solvent. Therefore, the solvent leaving the stripper of this invention has a larger quantity of dissolved butadiene than does the solvent leaving strippers used heretofore.

, By taking advantage of the additional stripping stage thus made available in the top of the desorber, a better `separation between the undesired hydrocarbon and butadiene is e'ected in a given number of theoretical 'stages in the stripper.

The following table illustrates the magnitude of the reduction in solvent circulation rate which may be obtained when extracting a feed containing -22 mol per cent butadiene under the conditions of this invention:

High Temp. Low Temp. Vap. Phase Vap. Phase Operation Operation Absorber 'lop Temp., F 44 25 Absorber Top Press., lbs/sq. in. gauge. 5 .0 Butodione Recovery, per cent of Butadiene in fresh feed 95 95 Solvent Circulation Rate, lbs. Solvent per lb. Feed -I. 32 13- This invention has particular application inthe extraction of butadiene from a dilute buta-l diene feed using ammoniacal cuprous acetate solvent. However. with modication, it might be applicable to other extraction systems, being different solvents. v

What is claimed lis:

ing the dissolved butadiene and butene after it has contacted and has been separated from the said mixture of hydrocarbons is stripped of butene by passing in countercurrent flow to the butadiene, the improvement which comprises heating the stripped ammoniacal cuprous solution to remove and separate a substantial fraction of the dissolved butadiene, passing the heated solution into the top section of a desorber above an upper plate thereof, removing the butadiene vapor from the top section of the desorber and, recycling this butadiene vapor for said stripping of the ammoniacal cuprous salt solution of the butene, passing the heated stripped ammoniacal cuprous acetate solution after the l separation of the first fraction of butadiene down said desorber in countercurrent iiow to a second fraction of butadiene obtained byfurther heating the heated stripped solvent to desorb the remaining fraction of butadiene in a lower part 'of' thedesorber below said upper plate of the said desorber, and removing this butadiene as a side stream from the desorber below said upper plate. v

2. In a process for the extraction of a dioleiin from a mixture of saturated and unsaturated hydrocarbons by means of ammoniacal cuprous acetate solution in which the 4ammoniacal cuprous acetate solution containing dissolved diolefin and monoolen after it has contacted and has been been separated from the said mixture of hydrocarbons is stripped of monoolen by passing in countercurrent flow to the dioleiin,

`the improvementv which comprises heating the stripped ammoniacal cuprous solution to remove and separate a substantial fraction of the dissolved diolefin, passing the heated solution into the top section of a desorber above an upper plate thereof, removing the dioleiln vapor from the top section of the desorber and recyclingvthis dioleiin vapor for said stripping of the ammoniacal cuprous acetate solution of the monoolen, passing the heated stripped ammoniacal cuprous acetate solution after separation of the rst fraction of diolen down said desorber in countercurrent ow to a second fraction of diolei'in obtained by further heating the 1. In a process for the extraction of butadiene from a mixture of hydrocarbons containing both butadiene and butene by means oi' an amheated stripped solvent to desorb the remaining fraction of dielen in a lower part of the desorber below said upper plate of the said desorber, and-removing this diolefin as a side stream from the desorber -below said upper plate.

RICHARD A. GIVEN. WILLIAM S. CRAFT.

REFERENCES CITED The following references are of record in the ille of this patent:

UNITED lSTATES PATENTS 

